EP2467218B1 - Procede de traitement d'une matiere alkaline particulaire carbonatable - Google Patents
Procede de traitement d'une matiere alkaline particulaire carbonatable Download PDFInfo
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- EP2467218B1 EP2467218B1 EP10754905.7A EP10754905A EP2467218B1 EP 2467218 B1 EP2467218 B1 EP 2467218B1 EP 10754905 A EP10754905 A EP 10754905A EP 2467218 B1 EP2467218 B1 EP 2467218B1
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- EP
- European Patent Office
- Prior art keywords
- treatment method
- carbonation
- oxidation
- granular
- bottom ash
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- 239000000463 material Substances 0.000 title claims description 59
- 238000000034 method Methods 0.000 title claims description 41
- 239000010882 bottom ash Substances 0.000 claims description 85
- 229910052782 aluminium Inorganic materials 0.000 claims description 78
- 239000004411 aluminium Substances 0.000 claims description 77
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 71
- 229910052751 metal Inorganic materials 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- 238000007254 oxidation reaction Methods 0.000 claims description 47
- 230000003647 oxidation Effects 0.000 claims description 46
- 239000008187 granular material Substances 0.000 claims description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- 239000007800 oxidant agent Substances 0.000 claims description 24
- 239000002699 waste material Substances 0.000 claims description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 238000010276 construction Methods 0.000 claims description 11
- 239000004568 cement Substances 0.000 claims description 10
- -1 permanganates Chemical class 0.000 claims description 9
- 238000005453 pelletization Methods 0.000 claims description 7
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 239000002609 medium Substances 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 56
- 229910001653 ettringite Inorganic materials 0.000 description 24
- 230000008961 swelling Effects 0.000 description 23
- 230000032683 aging Effects 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 10
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910021532 Calcite Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000920 calcium hydroxide Substances 0.000 description 6
- 235000011116 calcium hydroxide Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000001033 granulometry Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910001679 gibbsite Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000010813 municipal solid waste Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 238000004056 waste incineration Methods 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000010791 domestic waste Substances 0.000 description 3
- 230000033444 hydroxylation Effects 0.000 description 3
- 238000005805 hydroxylation reaction Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 230000000750 progressive effect Effects 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001398 aluminium Chemical class 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical class [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/021—Agglomerated materials, e.g. artificial aggregates agglomerated by a mineral binder, e.g. cement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
- B09B3/21—Agglomeration, binding or encapsulation of solid waste using organic binders or matrix
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/18—Carbon capture and storage [CCS]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to a method of treating a granular carbonatable material which contains aluminium metal and which has in particular a pH of at least 10.
- this treatment method at least a portion of the aluminium metal is oxidised by contact with moisture.
- waste materials is alkaline and comprises carbonatable substances, such as calcium and/or magnesium oxides and/or hydroxides. It is known that the carbonation of these substances, in particular calcium hydroxide, makes it possible to obtain materials having good mechanical qualities, as well as a better retention of pollutants, in particular heavy metals, present in such waste and posing significant problems for the elimination thereof.
- waste incinerator bottom ashes (MWI-bottom ashes)
- Municipal waste incinerator bottom ash consists principally of non-combustible coarse material and unburnt organic matter collected in a cooling basin at the discharge from a combustion chamber of an incinerator. They are composed of solid phases formed at high temperature, some of which are maintained in a metastable state following the rapid cooling of the materials emerging from the combustion chamber.
- To reprocess the bottom ash it is generally subjected to a separation of the aluminium metal by eddy currents, followed by natural aging (weathering) of several months. During this aging, a complex series of several interconnected chemical phenomena takes place.
- the aging of the bottom ash is particularly required to reduce the problems of swelling that may occur when bottom ash is used in construction, in particular as a road foundation (lean concrete) or even as a granulate in concrete.
- the bottom ash comprises aluminium, a significant proportion of which is in its elementary form, i.e. in the form of aluminium metal. Because of the high pH of the bottom ash, and the relatively low redox potential of aluminium, aluminium metal is oxidised and reacts with hydroxyl ions during the aging process to form aluminates which are further precipitated into expansive Al(OH) 3 .
- Al(OH) 3 formation in the bottom ash during aging is important to avoid problems of swelling when the bottom ash is used as an aggregate. This is because, when the aluminium is not previously corroded or even better passivated with a coating covering it, the subsequent hydroxylation thereof will produce swelling. Moreover, when used as aggregate in concrete the oxidation reaction of the aluminium metal as a result of the high pH of fresh and especially of setting concrete will produce hydrogen gas forming gas bubbles in the concrete and reducing thus the strength thereof. As described in " Aggregate cement reactions in MWI-bottom ash-based concrete - a petrographical assessment", B. Laenen, R. Dreesen and D.
- the bottom ash is initially highly alkaline (pH ⁇ 11 to 12), the carbonation thereof, in particular the carbonation of portlandite, will therefore lower the pH.
- This acidification following the progressive carbonation of the portlandite will cause a precipitation of the dissolved aluminium forming an aluminium hydroxide gel [Al(OH) 3 ] causing a swelling of the material.
- the objective of the natural aging of bottom ashes is not only a progressive carbonation of the portlandite but also and in particular a dimensional and mineralogical stabilisation of the bottom ash.
- One drawback of accelerated carbonation is therefore that, unlike prolonged natural aging, an accelerated carbonation does not result in the same dimensional and mineralogical stabilisation and is not in a position to solve the problems of swelling of carbonated materials, in particular carbonated bottom ash.
- bottom ashes When bottom ashes, whether they are carbonated or not, are used as aggregate in concrete, the aluminium metal present therein reacts with the alkaline water contained in the fresh and especially in the setting concrete to produce hydrogen gas.
- the problem of this hydrogen gas production is described in the publication " MSWI ashes as mineral additions in concrete", L. Bertolini, M. Carsanaa, D. Cassagoa, A. Quadrio Curziob and M. Collepardia, Cement and Concrete Research, Vol. 34, No. 10, October 2004, pp. 1899-1906 .
- Aluminium corrosion tests are described in this article which demonstrate that at a pH of 11.5 a metal aluminium plate corrodes at a rate of about 1 mg/m 2 /day whereas at a pH of about 12.5 it corrodes at a rate which was about 100 times greater and at a pH of 13 - 13.5 at a rate which was even about 1000 times greater.
- the bottom ashes were ground very finely (average particle size of about 3 ⁇ m) so that the aluminium metal had a large available surface, the bottom ashes required a couple of days to a couple of months of rest to end the gas development.
- the authors thus suggested investigating some factors which might influence the time for the exhaustion of the hydrogen evolution reaction, such as the fineness of the MSWI bottom ash particles, the temperature, the stirring conditions and a higher pH.
- a drawback of this method is that a relatively large amount of NaOH is required to raise the pH to increase the corrosion rate of the aluminium metal but that even at that high pH it takes quite a lot of time to oxidise a major part of the aluminium in view of the large particle size (and thus the relatively small surface area). Moreover, at this high pH the ettringite remains in the bottom ash and can thus still cause swelling phenomena when the pH of the bottom ashes drops, which will be especially the case when the bottom ashes are used as construction aggregates in layers which are not bonded by means of cement so that their pH may drop more quickly.
- a further drawback is that under the very alkaline conditions of the alkaline granular material, the glass cullet contained therein (in particular in bottom ashes) will promote the alkali silicate reaction associated with the formation of an expansive silica gel.
- Figure 1 shows a titration graph obtained by titrating a slurry composed of 100 grams of crushed bottom ashes mixed with 100 ml of distilled water with a 1M sodium hydroxide solution (pH 14). It can be seen that the pH of the slurry is considerably lower than the pH which can be calculated based on the dilution of the 1 M NaOH solution in the distilled water (the dilution of 100 ml 1 M NaOH solution in 100 ml of distilled water would result for example in a concentration of 0.5 M, or a pH of about 13.7, instead of the observed pH of about 12.8) so that it takes quite a lot of NaOH to increase the pH of the bottom ashes to such an extent that a high aluminium oxidation speed is achieved.
- Figure 1 shows that the bottom ash contains substances which are acidic with respect to hydroxide at those high pH values providing a "buffering" effect so that reaction of these substances with hydroxide requires extra sodium hydroxide.
- Figure 2 is a same titration graph as Figure 1 , but the titration has been done with 10M NaOH (about 400 g NaOH/I) instead of with 1 M NaOH.
- the aluminium metal particles/inclusions will also be much bigger and will thus provide a considerably smaller surface area so that the time needed to corrode the aluminium will also be in the same order of magnitude, more particularly in the order of magnitude of days or even months.
- supposing a cylindrical shape of the aluminium particles/inclusions when these particles/inclusions are 1000 times larger, their surface area, and hence their oxidation speed, will be 1000 times smaller.
- the method described in the present disclosure addresses the above described problems by proceeding not only with an oxidation step wherein aluminium metal is oxidised but also with a carbonation step wherein the alkaline granular carbonatable material is at least partially carbonated by means of carbon dioxide, the oxidation step being accelerated by providing at least one oxidising agent, which has a higher redox potential than the water contained in the moisture which is in contact with the aluminium metal, in this moisture.
- moisture is to be understood the liquid contained in the pores of the granular material and/or adhered to the granular material and, when the granular material is combined with more liquid than the liquid contained therein or adhered thereto, also the liquid wherein the granular material is embedded (in particular as a slurry or a dispersion).
- the oxidising agent Due to the fact that the oxidising agent has a higher redox potential than the water contained in the moisture which is in contact with the aluminium metal (under the actual oxidation conditions), which moisture will be alkaline due to the alkaline nature of the granular material, no hydrogen gas will be liberated by the reaction of water (reduction) with aluminium metal in accordance with the following oxido-reduction reaction:
- An important advantage of the use of an oxidising agent is that the pH of the moisture contained in the granular material does not have to be raised in order to increase the oxidation rate. Compared to the amount of NaOH, less moles of the oxidising agent are thus needed. Moreover, since ettringite is formed under alkaline conditions, no or less ettringite will be formed in the carbonatable material during the oxidation step.
- the carbonation step is further intended to lower the pH of the granular material so that the formation of ettringite is avoided or so that any ettringite contained in the granular material is destabilised.
- the accelerated oxidation of the aluminium metal transforms at least part of the aluminium metal into aluminium oxide and/or creates layers of aluminium oxide and/or hydroxide around metal aluminium particles. Not only do these layers become substantially inert but they also protect the cores of the particles, which remain in the metal state, limiting the release of Al 3+ ions, and therefore the subsequent formation of aluminium hydroxide.
- alkaline granular carbonatable material is carbonated until it has a pH lower than 10, preferably lower than 9.5 and more preferably lower than 9.
- ettringite is not formed and is not stable so that the carbonated material doesn't contain any ettringite.
- the granular material contains ettringite, usually as a neoformed phase formed in an alkaline environment in the presence of sulphate and aluminium ions, this ettringite will release aluminium ions when the pH of the granular material drops below 10, which aluminium ions may subsequently form an aluminium hydroxide gel causing an undesirable swelling of the material.
- Accelerated oxidation may be effected before, after and/or simultaneously with accelerated carbonation.
- the accelerated oxidation is however preferably performed after (or during) the accelerated carbonation so that the pH of the granular material has already been lowered and so that consequently the passivation of the aluminium metal may be more effective because of the lowering of the pH obtained during the carbonation.
- aluminium metal is passivated rather than oxidised whilst above this pH value aluminium metal will rather corrode without forming a passivating coating.
- the oxidised aluminium will be in the form of more water-soluble Al ⁇ OH 4 - ions whilst at lower pH values aluminium metal is oxidised immediately in the substantially water-insoluble Al(OH) 3 form forming a passivation layer.
- said oxidising agent is chosen from the group comprising hypochlorites, peroxides, permanganates, perchlorates and perborates, as well as combinations of same, so as to accelerate the oxidation rate compared with oxidation by natural aging.
- said oxidising agents could be dissolved in an aqueous medium which is applied onto the alkaline granular material.
- This aqueous medium, applied to the granular material can thus assist in obtaining the optimum moisture content for its subsequent accelerated carbonation.
- the aqueous medium is preferably sprayed onto the granular material.
- NaOH is used to oxidise the aluminium metal
- such a spray process is not possible in view of the too high concentration of NaOH required to raise the pH (too viscous and too aggressive liquid).
- the moisture content of the granular material is less than 90 % by dry weight, preferably less than 70 % by dry weight and more preferably less than 50 % by dry weight during the accelerated oxidation.
- These low moisture contents accelerate the carbonation step and are easily obtained in the process according to the invention since only a small amount of the (dissolved) oxidising agent needs to be applied (in particular sprayed) onto the granular material.
- said carbonation may be performed in a rotary drum.
- a rotary drum facilitates diffusion of the carbonation agent in the carbonatable material.
- the granular material may contain more water, and may in particular even be saturated with moisture.
- said carbonation may be performed with carbon dioxide, preferably with gaseous carbon dioxide, and more particularly in an atmosphere enriched with gaseous carbon dioxide.
- an atmosphere could contain for example combustion gases or gases resulting from industrial processes producing carbon dioxide.
- this process could serve to substantially reduce the greenhouse gas emissions and provides a cheap method for lowering the pH of the granular material in view of destabilising ettringite and/or preventing the formation thereof (by lowering the pH of the fresh material, in particular the fresh bottom ash, before secondary ettringite will be formed therein under the alkaline conditions of the fresh material).
- the carbonation is accelerated by treating the alkaline granular carbonatable material with a medium containing more than 1 wt. %, preferably more than 5 wt. % and more preferably more than 10 wt. % of carbon dioxide, which medium is preferably a gas.
- said carbonatable material could contain at least one waste material, which would thus be reprocessed as raw material while encapsulating any contaminants, such as heavy metals, contained therein.
- the waste material could itself be carbonatable, but a carbonatable binder, such as cement, could also be added thereto.
- said waste material could contain at least bottom ash, for example municipal waste incinerator bottom ash.
- bottom ash normally contains both carbonatable components, including in particular portlandite, and aluminium metal and ettringite, as well as heavy metals.
- the method disclosed here would thus make it possible to obtain a material that could be used in construction and is stable (even when the pH is lowered to a pH value of less than 10) and in which the heavy metals would be immobilised.
- the processing method could also comprise a prior step of separating some of the aluminium metal by eddy currents.
- the aluminium metal content and therefore also the associated swelling phases could be reduced in this prior step.
- the method would thus enable the economical recovery of part of the aluminium metal, a material with a high commercial value and the production of which requires very significant contributions of energy and is a significant source of greenhouse gas emissions.
- the granular carbonatable material still comprises at the start of said oxidation step at least 0.1 % by dry weight, in particular at least 0.3 % by dry weight and more particularly at least 0.5 % by dry weight of aluminium metal.
- the carbonatable material could have a moisture content of between 10% and 15% by weight.
- a moisture content in this range, and in particular around 12%, facilitates the carbonation of the carbonatable material by the diffusion of carbon dioxide in the water.
- said carbonatable material could be in the granular state.
- Such a granular state facilitates both the physical handling of this material and the chemical processing thereof by accelerated oxidation and carbonation.
- said granular carbonatable material may contain particles with a size greater than 1 mm, preferable greater than 2 mm, and even more preferably greater than 4 mm, and this at least during the carbonation and the oxidation step.
- the processing method could also comprise a pelletisation step wherein grains of said carbonatable material would be agglomerated so as to obtain a coarser granular material. In this way, it becomes possible to adjust the granulometry of the material resulting from the processing of granular material with a very fine granulometry to its subsequent application as an aggregate.
- said pelletisation step could be prior to the accelerated carbonation.
- the grains agglomerated in the pelletisation step could be bonded to one another by the carbonates formed during the accelerated carbonation.
- the pelletisation could also be simultaneous with the carbonation, so that the agglomerated grains are bonded by successive layers of carbonates.
- the present disclosure also concerns a method which comprises the further step of using the carbonated and oxidised granular material as a construction aggregate to produce a layer which is not bonded by means of cement, or more generally by means of a hydraulic binding agent.
- the layer may in particular be a sub-base layer, in particular a sub-base layer of a road construction.
- Municipal waste incinerator bottom ash (MWI-bottom ash), as illustrated in Figure 3 , consists essentially of mineral material and is like a greyish gravel in which residues such as bottle glass, ceramics, scrap iron and non-ferrous metals can be identified.
- composition of the bottom ash therefore proves to be extremely complex and, among the main constituents, there are generally:
- the purpose of this aging processing of the MWI-bottom ash is intended firstly to stabilise it in particular on a dimensional level and secondly to fix the heavy metals within the neoformed phases. This is because the carbonates, in precipitating, are liable to trap the trace elements such as cadmium, lead and zinc whereas the same elements with in addition copper and manganese appear to have great affinity for the iron and aluminium (hydr)oxides.
- bottom ash If the bottom ash is used without sufficient aging, swelling phenomena caused in particular by the subsequent formation of aluminium hydroxides from aluminium metal and ettringite still present in the bottom ash may take place.
- the deleterious effects of these phenomena on for example a road 3 having a base layer 4 comprising bottom ash are illustrated in Figure 4 .
- the aluminium hydroxides 5 precipitating around the aluminium metal particles 6 cause swelling and cracks 7 both in the base layer 4 and in the bituminous concrete topping 8.
- the bottom ash is first of all subjected to an initial step of separation of aluminium metal by eddy currents, in the same way as in the conventional treatment of bottom ash, in order to recover a large proportion of this aluminium.
- the thus obtained bottom ash still contains at least 0.1 % by dry weight, in particular at least 0.3 % by dry weight and more particularly at least 0.5 % by dry weight of aluminium metal. Usually it contains between 0.8 and 2.5 % by dry weight of aluminium metal.
- one or more oxidising agents such as sodium hypochlorite, hydrogen or calcium peroxides, potassium permanganate and/or sodium perborate are added to the municipal waste incinerator bottom ash before accelerated carbonation thereof in a rotary drum.
- the oxidising agents may be added in the form of an aqueous solution, serving at the same time to raise the moisture content of the bottom ash.
- a relatively small amount of aqueous solution is used so that the moisture content of the granular material is less than 90 % by dry weight, preferably less than 70 % by dry weight and more preferably less than 50 % by dry weight during the accelerated oxidation.
- the moisture content of the granular material doesn't need to be lowered before the carbonation step in order to achieve a high carbonation rate.
- the optimum moisture content is approximately 12% by weight of bottom ash but especially when performing the carbonation step in a rotary drum, higher moisture content have no major effect on the carbonation rate.
- This aqueous solution of oxidising agent may contain for example 1% by weight oxidising agent with respect to the dry bottom ash weight and is preferably sprayed onto the bottom ash. Due to the alkaline nature of the bottom ash, the moisture contained therein will usually be alkaline, even when the aqueous solution of the oxidising agent which is applied onto the bottom ash may be (somewhat) acidic.
- the bottom ash is subjected to an accelerated dynamic carbonation in a rotary drum for 4 to 5 hours.
- Combustion gases such as for example household waste incineration fumes, are introduced into the drum in order to obtain a hot atmosphere (approximately 50°C) enriched with carbon dioxide (approximately 10% to 12%).
- a humidity level equal to or greater than 80% is maintained in the atmosphere of the drum rather than the usual 30% of household waste incineration fumes.
- the bottom ash has a pH lower than 10, preferably lower than 9.5 and more preferably lower than 9.
- the bottom ash had a pH of 8.2 (test performed with hydrogen peroxide) and 8.9 (test performed with sodium hypochlorite), which pH is similar both to that of bottom ash naturally matured for several months, and to that of bottom ash subjected to accelerated carbonation without prior oxidation. The carbonation does not therefore appear to be substantially affected by the oxidising agent.
- the bottom ash treated in this way has a dimensional stability substantially superior to that of bottom ash treated solely by accelerated carbonation, and thus makes it possible to comply with the strict standards for construction, such as for example those for the use of bottom ash in foundation layers, subgrades (lean concrete) and fill in road construction.
- the pH of the granular material is measured in accordance with the standard DIN 38414-S4
- the oxidising agents instead of adding the oxidising agents before the accelerated carbonation, it is also possible to add them after this carbonation. This may be advantageous since passivation of aluminium metal is assisted at lower pH values.
- the pH of the moisture which is in contact with the aluminium metal is therefore preferably lowered before the oxidation step to a pH value lower than 9. This is preferably done by performing the carbonation step at least partially before and/of during the oxidation step.
- the oxidising agents may also be partially added before and after the accelerated carbonation, thus combining the advantages of more effective oxidation under more alkaline conditions and more effective passivation under less alkaline conditions.
- the moisture content of the granular material is preferably less than 90 % by dry weight, more preferably less than 70 % by dry weight and most preferably less than 50 % by dry weight.
- the oxidising agent is more concentrated thus increasing the oxidation rate.
- the material needs less or even no drying after the oxidation step, in particular when performing the carbonation step after the oxidation step.
- the granulometry of the resulting material may normally be simply adjusted by screening of the treated material, in particular in such a way that the carbonatable material contains particles with a size greater than 1 mm, preferable greater than 2 mm, and even more preferably greater than 4 mm
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Claims (18)
- Procédé de traitement d'une matière granulaire alcaline carbonatable qui contient de l'aluminium métallique et qui a en particulier un pH d'au moins 10, lequel procédé comprend une étape d'oxydation dans laquelle au moins une partie dudit aluminium métallique est oxydé par contact avec de l'humidité et lequel procédé comprend une étape de carbonatation dans laquelle la matière granulaire carbonatable est au moins en partie carbonatée, caractérisé en ce que ladite oxydation est accélérée en prévoyant au moins un agent oxydant dans ladite humidité, lequel agent oxydant a un potentiel redox plus élevé que l'eau contenue dans ladite humidité.
- Procédé de traitement selon la revendication 1, dans lequel la matière granulaire alcaline carbonatable est carbonatée jusqu'à ce qu'elle ait un pH inférieur à 10, de préférence inférieur à 9,5 et mieux encore inférieur à 9.
- Procédé de traitement selon la revendication 1 ou 2, dans lequel ladite carbonatation est effectuée avec du dioxyde de carbone, de préférence avec du dioxyde de carbone gazeux.
- Procédé de traitement selon la revendication 3, dans lequel ladite carbonatation est accélérée en traitant la matière granulaire alcaline carbonatable avec un milieu contenant plus de 1 % en poids, de préférence plus de 5 % en poids et mieux encore plus de 10 % en poids de dioxyde de carbone, lequel milieu est de préférence un gaz.
- Procédé de traitement selon l'une quelconque des revendications 1 à 4, dans lequel ledit agent oxydant est choisi dans le groupe comprenant des hypochlorites, des peroxydes, des permanganates, des perchlorates et des perborates ainsi que des combinaisons de ceux-ci.
- Procédé de traitement selon l'une quelconque des revendications 1 à 5, dans lequel ledit agent oxydant est dissous dans un milieu aqueux qui est appliqué, de préférence vaporisé, sur la matière granulaire alcaline.
- Procédé de traitement selon l'une quelconque des revendications 1 à 6, dans lequel ladite oxydation accélérée est au moins en partie effectuée après avoir abaissé le pH de ladite humidité à un pH inférieur à 9.
- Procédé de traitement selon la revendication 7, dans lequel le pH de ladite humidité est abaissé à un pH inférieur à 9 en effectuant l'étape de carbonatation au moins en partie avant et/ou pendant l'étape d'oxydation.
- Procédé de traitement selon l'une quelconque des revendications 1 à 8, dans lequel ladite oxydation accélérée est au moins en partie effectuée avant la carbonatation.
- Procédé de traitement selon l'une quelconque des revendications 1 à 9, dans lequel la teneur en humidité de la matière granulaire est inférieure à 90 % en poids sec, de préférence inférieure à 70 % en poids sec et mieux encore inférieure à 50 % en poids sec pendant l'oxydation accélérée.
- Procédé de traitement selon l'une quelconque des revendications 1 à 10, dans lequel ladite carbonatation est effectuée dans un tambour rotatif.
- Procédé de traitement selon l'une quelconque des revendications 1 à 11, dans lequel ladite matière granulaire carbonatable contient au moins des mâchefers, en particulier des mâchefers d'incinération d'ordures ménagères.
- Procédé de traitement selon l'une quelconque des revendications 1 à 12, comprenant également une étape antérieure consistant à éliminer une partie de l'aluminium métallique par des courants de Foucault.
- Procédé de traitement selon l'une quelconque des revendications 1 à 12, dans lequel ladite matière granulaire carbonatable contient au début de ladite étape d'oxydation au moins 0,1 % en poids sec, en particulier au moins 0,3 % en poids sec et plus particulièrement au moins 0,5 % en poids sec d'aluminium métallique.
- Procédé de traitement selon l'une quelconque des revendications 1 à 14, dans lequel ladite matière carbonatable est à l'état granulaire pendant ladite étape de carbonatation et pendant ladite étape d'oxydation, et comprend pendant ces étapes des particules d'une taille supérieure à 1 mm.
- Procédé de traitement selon la revendication 15, dans lequel la matière carbonatable contient des particules d'une taille supérieure à 2 mm et de préférence d'une taille supérieure à 4 mm pendant les étapes de carbonatation et d'oxydation.
- Procédé de traitement selon l'une quelconque des revendications 1 à 16, comprenant en outre une étape de pelletisation pendant laquelle les particules de ladite matière carbonatable sont agglomérées de manière à obtenir une matière granulaire plus grossière, laquelle étape de pelletisation est effectuée avant et/ou pendant l'étape de carbonatation.
- Procédé de traitement selon l'une quelconque des revendications 1 à 17, comprenant l'étape supplémentaire d'utilisation de la matière granulaire carbonatée et oxydée comme agrégat de construction pour produire une couche qui n'est pas liée au moyen de ciment.
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PL10754905T PL2467218T5 (pl) | 2009-08-21 | 2010-08-23 | Sposób obróbki alkalicznego granulowanego materiału zdolnego do karbonizacji |
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BE2009/0514A BE1018866A3 (fr) | 2009-08-21 | 2009-08-21 | Procede de traitement d'une matiere carbonatable. |
PCT/EP2010/062276 WO2011020927A2 (fr) | 2009-08-21 | 2010-08-23 | Procédé de traitement d'une matière granulaire alcaline apte à être carbonatée |
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US (1) | US8603419B2 (fr) |
EP (1) | EP2467218B2 (fr) |
BE (1) | BE1018866A3 (fr) |
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WO2009132692A1 (fr) * | 2008-04-28 | 2009-11-05 | Carbstone Innovation Nv | Fabrication d'un article par carbonatation de matières alcalines |
ITVE20110041A1 (it) * | 2011-05-31 | 2012-12-01 | Veneta Depuratori E Affini S Ve D A Soc | Procedimento di trattamento di ceneri pesanti o scorie in genere.- |
CA2852805A1 (fr) | 2011-10-20 | 2013-04-25 | Recmix Belgium | Procede de recyclage des eaux usees a partir d'un processus de traitement d'une scorie d'acier inoxydable |
CN104039735B (zh) * | 2011-10-26 | 2017-04-26 | 碳石创新公司 | 制备含有模压的、碳酸化的粒状材料的粘结制品的方法 |
US20150117953A1 (en) * | 2012-03-30 | 2015-04-30 | Yoshino Gypsum Co., Ltd. | Insolubilizing agent for specific toxic substances, method for insolubilizing specific toxic substances using same, and soil improving method |
AU2015263983A1 (en) * | 2014-05-22 | 2016-12-22 | Tav Holdings, Inc. | System and method for recovering metals from a waste stream |
FR3127942A1 (fr) * | 2021-10-08 | 2023-04-14 | Eurovia | Utilisation de mâchefers d’incineration de dechets non dangereux dans des usages betons |
CN114715905B (zh) * | 2022-04-20 | 2023-03-10 | 河南理工大学 | 一种高碳化活性硅灰石及其制备方法和应用 |
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SE364699B (fr) † | 1972-07-13 | 1974-03-04 | Cementa Ab | |
US5362319A (en) † | 1992-10-23 | 1994-11-08 | Johnson William B | Process for treating fly ash and bottom ash and the resulting product |
NL9202033A (nl) † | 1992-11-23 | 1994-06-16 | Tauw Milieu Bv | Werkwijze voor de behandeling van verbrandingsresiduen en de toepassing daarvan als adsorptiemiddel. |
JPH09285773A (ja) † | 1996-04-23 | 1997-11-04 | Kanegafuchi Chem Ind Co Ltd | 廃棄物処理剤および処理方法 |
DK90796A (da) † | 1996-08-28 | 1998-03-01 | Thomas Hoejlund Christensen | Metode til udvaskning og kemisk stabilisering af flyveaske, røgrensningsprodukter og andre metalholdige materialer |
FR2755884B1 (fr) * | 1996-11-15 | 1999-03-19 | Lefebvre Jean Ets | Procede de traitement des machefers pour l'obtention de grave-mousse |
US20030227814A1 (en) † | 2002-06-10 | 2003-12-11 | Michael Priesnitz | Lightweight aggregate |
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ITMI20071002A1 (it) * | 2007-05-17 | 2008-11-18 | Petracem Srl | Manufatto per edilizia. |
GB0716360D0 (en) | 2007-08-22 | 2007-10-03 | Univ Greenwich | Production of secondary aggregates |
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EP2467218A2 (fr) | 2012-06-27 |
EP2467218B2 (fr) | 2017-06-21 |
ES2493721T5 (es) | 2017-10-10 |
BE1018866A3 (fr) | 2011-10-04 |
WO2011020927A2 (fr) | 2011-02-24 |
PL2467218T3 (pl) | 2014-10-31 |
ES2493721T3 (es) | 2014-09-12 |
US8603419B2 (en) | 2013-12-10 |
US20120195814A1 (en) | 2012-08-02 |
WO2011020927A3 (fr) | 2011-09-09 |
PL2467218T5 (pl) | 2017-10-31 |
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